3 4 4-trifluoro-3-butenylthio methylidene compounds and their utility

ABSTRACT

COMPOUNDS OF THE FORMULA   CF2=CF-CH2-CH2-S-C(=X)-R   WHEREIN X IS A MEMBER SELECTED FROM THE GROUP CONSISTING OF OXYGEN, SULFUR, IMINO, PHENYLIMINO, CHLOROPHENYLIMINO, ALKYLIMINO CONTAINING FROM 1 TO 8 CARBON ATOMS, INCLUSIVE, AND ALKENYLIMINO CONTAINING 2 TO 4 CARBON ATOMS, INCLUSIVE, R IS SELECTED FROM THE GROUP   -N(-R1)-R2 AND -S-R3   WHEREIN R1 AND R2, INDIVIDUALLY, ARE SELECTED FROM THE GROUP CONSISTING O HYDROGEN, ALKYL CONTAINING FROM 1 TO 10 CARBON ATOMS, INCLUSIVE, HYDROXYALKYL CONTAINING FROM 1 TO 4 CARBON ATOMS, INCLUSIVE, ALKENYL CONTAINING FROM 2 TO 4 CARBON ATOMS, INCLUSIVE, CYCLOALKYL CONTAINING FROM 4 TO 6 CARBON ATOMS, INCLUSIVE, PHENYL, R1 AND R2 JOINTLY ARE A DIVALENT ALKYLENE RADICAL CONTAINING 4 TO 6 CARBON ATOMS, INCLUSIVE, AND R3 IS SELECTED FROM THE GROUP LOWER ALKYL, CHLOROPHENYL LOWER ALKYL, AND 3,4,4-TRIFLUORO3-BUTENYL. THE ABOVE COMPOUNDS ARE EFFECTIVE HERBICIDES AND NEMATOCIDES.

Patented Apr. 4, 1972 6 Claims ABSTRACT OF THE DISCLOSURE Compounds ofthe formula wherein X is a member selected from the group consisting ofoxygen, sulfur, imino, phenylimino, chlorophenylimino, alkyliminocontaining from 1 to 8 carbon atoms, inclusive, and alkenyliminocontaining 2 to 4 carbon atoms, inclusive, R is selected from the group31 N and S R wherein R and R individually, are selected from the groupconsisting of hydrogen, alkyl containing from 1 to carbon atoms,inclusive, hydroxyalkyl containing from 1 to 4 carbon atoms, inclusive,alkenyl containing from 2 to 4 carbon atoms, inclusive, cycloalkylcontaining from 4 to 6 carbon atoms, inclusive, phenyl, and R and Rjointly are a divalent alkylene radical containing 4 to 6 carbon atoms,inclusive, and- R is selected from the group lower alkyl, chlorophenyllower alkyl, and 3,4,4-t1ifluoro- 3-butenyl. The above compounds areeffective herbicides and nematocides.

This application is a division of copending application Ser. No.735,495, filed May 27, 1968, now U.S. Pat. 3,510,503, which applicationis a continuation in part of copending application Ser. No. 491,508,filed Sept. 27, 1965, now abandoned.

This invention relates to certain new substituted 3,4,4-trifluoro-3-butenylthio methylidene compounds and to the utility of saidcompounds as nematocides and herbicides. More specifically, thisinvention relates to compounds of the general formula wherein X is amember selected from the group consisting of oxygen, sulfur, imino,phenylimino, chlorophenylimino, alkylimino containing from 1 to 8 carbonatoms, inclusive, and alkenylimino containing 2 to 4 carbon atoms,inclusive; R is selected from the group 1 -N and -SR wherein R and Rindividually, are selected from the group consisting of hydrogen, alkylcontaining from 1 to 10 carbon atoms, inclusive, hydroxyalkyl contammgfrom 1 to 4 carbon atoms, inclusive, alkenyl containing from 2 to 4carbon atoms, inclusive, cycloalkyl containing from 4 to 6 carbon atoms,inclusive, phenyl, and R and R jointly are a divalent alkylene radicalcontaining 4 to 6 carbon atoms, inclusive, and R is selected from thegroup lower alkyl, chlorophenyl lower alkyl, and 3,4,4-trifluoro-3-butenyl.

In the above description, the following preferred embodiments areintended for the various groups: in alkylimino such alkyl members ascontaining from 1 to about 8 carbon atoms in both straight chain andbranched chain configurations, for example, methyl, ethyl, propyl,butyl, amyl, hexyl, octyl, isooctyl and 2,2-dimethy1butyl; inalkenylimino, such alkenyl members as containing from 2 to about 4carbon atoms, inclusive, for example vinyl, allyl, butenyl and the like.The term alkyl preferably includes those members of the group whichcontain 1 to about 10 carbon atoms, inclusive, in both straight chainand branched chain configurations. Preferable embodiments of the termalkyl as used herein are, for example, methyl, ethyl, propyl, butylpentyl, hexyl, heptyl, octyl, nonyl, decyl, neopentyl, isopentyl,sec-butyl, isobutyl, tert-butyl, l-methylpentyl, 1,1-dirnethylpentyl,1,2-dimethylpropyl, l,1,2,2-tetramethyl propyl, 1,1-dimethy1 butyl,1,1-dimethyl pentyl, 1,1-trimethyl butyl, l-ethylbutyl andl-ethylpentyl. The term hydroxyalkyl, preferably includes those membersof the group which contain from 1 to about 4 carbon atoms, inclusive,for example hydroxyrnethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl.The term cycloalkyl preferably includes those members of the group whichcontain from about 4 to about 6 carbon atoms, inclusive, for example,cyclobutyl, cyclopentyl and cyclohexyl. The term lower alkyl preferablyincludes members of the group in which the lower alkyl group containsfrom 1 to about 6 carbon atoms inclusive, in both straight chain andbranched chain configurations, for example, methyl, ethyl, propyl,butyl, pentyl, hexyl, isopropyl, isobutyl, tert-butyl, l-methylpentyl,1,2-dimethylpropyl, neopentyl and isopentyl. The term chlorophenyl loweralkyl preferably includes those members of the group which contain 1 toabout 2 carbon atoms in the lower alkyl group, for example,chlorophenylmethyl and chlorophenylethyl. The phrase R and R jointly area divalent alkylene radical containing 4 to '6 carbon atoms preferablyincludes such groups as tetramethylene, pentamethylene andhexamethylene.

The compounds herein disclosed are prepared by various methods. One suchgeneral method applied in preparing the compounds was the condensationof the appropriate mercaptan and carbon disulfide in the presence ofbasic catalyst followed by the addition of 1,1,2-trifluoro-4-bromobutene-1. Similarly, some of the compounds may beprepared by the condensation of a substituted amine, carbon disulfideand 1,1,2-trifluoro-4- bromobutene-l. In the same manner, a substitutedthiourea may be condensed with 1,1,2-trifluoro-4-bromobutene-l, andlikewise a secondary amine, carbon oxysulfide and1,1,2-trifluoro-4-bromobutene-1 may be reacted to produceN,N-disubstituted-S-triiluorobutenyl thiocarbamates. The reactionsproceed readily in the liquid phase and which are between roomtemperature and reflux temperature of the solvent, if any is used, areemployed. Preferably, the reaction mixture is refluxed, usually at anelevated temperature.

It has been found that the compounds of the present invention areparticularly effective as nematocides and herbicides. They are eifectivein the control of nematodes which applied to a nematodal habitat.

The method of the present invention of controlling undesirablevegetation comprises applying an herbicidally effective amount of theabove-described compounds to the area where control is desired. Anherbicide is used herein to mean a compound which controls or modifiesthe growth of plants. By an herbicidally etfective amount is meant anamount of compound which causes a modifying effect upon the growth ofplants. Such modifying effects include all deviations from naturaldevelopment, for example, killing, retardation, defoliation,desiccation, regulation, stunting, tillering, stimulation, dwarfing andthe like. By plants it is meant germinant seeds, emerging seedlings, andestablished vegetation including the roots and above-ground portions.

The compounds of the present invention may be prepared in accordancewith the following illustrative examples.

EXAMPLE 1 Preparation of S,S-bis-(3,4,4-trifluoro-3-butenyl)N-ethylimino dithiocarbonate Ethylamine (9.0 g.) and triethylarnine(40.4 g.) were placed in a flask and 15.2 g. of carbon disulfide wasadded dropwise. The flask and its contents during the addition were keptat a temperature of l-20 C. and then stirred for 30 minutes at C.1,1,2-trifluoro-4-bromobutene-1 was added and the reaction mixtureheated at 60 C. for 1:2 hours.

Recovery of the product was accomplished by pouring the reaction mixtureinto water and extracting with benzene. The benzene was washed withwater and dried with anhydrous calcium chloride. The benzene solutionwas filtered and the solvent removed. There was obtained 9 51.8 g. (77%)of the title compound, a yellow liquid,

B.P. 87 C./0.1 mm., 11 1.5249.

Analysis.Calculated for C I-I F NS (percent): Carbon, 45.5; hydrogen,4.7. Found (percent): Carbon, 45.0;

hydrogen, 5.20.

EXAMPLE 2 Preparation of 3,4,4-trifiuoro-3-butenyl ethyltrithiocarbonate In the same manner as Example 1, ethyl mercaptan (6.2g.) and triethylamine (10.1 g.) were dissolved in 150 ml. of dioxane.Carbon disulfide (7.6 g.) was then added to the mixture at a temperatureheld between 20-30 C. The reaction mixture was heated to 45 C. forminutes, 1,1,Z-trifiuoro-4-bromobutene-1 (18.9 g.) was added and themixture was stirred and heated to 60 C. for about an hour. It was thenpoured into water and the product recovered in benzene, as described inExample 1. There was obtained 8.5 g. of the product, B.P. 6970 C./0.1mm.

Analysis.-Calculated for CqH9F S (percent): Carbon, 34.0; hydrogen, 3.7.Found (percent): Carbon, 34.7; hydrogen, 4.0.

EXAMPLE 3 Preparation of S-(3,4,4-trifluoro-3-butenyl) N-phenyl-N-methylisothiourea l-methyLl-phenyl thiourea (16.6 g.) and1,1,2-trifluoro-4-bromobutene-1 (18.9 g.) were heated under reflux forthree hours in 100 ml. of nitromethane as solvent. The solvent wasremoved under reduced pressure. The residue was taken up in water andneutralized with cold potassium hydroxide. The product was extractedwith benzene, dried over anhydrous calcium chloride and the solventremoved by evaporation. There was obtained 19.7 g. of the titlecompound, n 1.5339.

Analysis.Calculated for C H F N S (percent): Carbon, 53.0; hydrogen,4.8; nitrogen, 10.2. Found (percent): Carbon, 53.4; hydrogen, 5.2;nitrogen, 10.1.

The following is a table of the compounds prepared according to theaforedescribed procedures. Compound numbers have been assigned to eachcompound and are then used for identification throughout the balance ofthe application.

TABLE I 1 Prepared in Example 1. 2 Prepared in Example 2. 3 Prepared inExample 3. 4 on.

5 Liquid.

Other examples of compounds falling within the generic formula presentedherein and which may be formulated into herbicidal and nematocidalcompositions and applied as herein illustrated are:

3 ',4',4'-trifl-uoro-3 '-butenyl-3-p-chlorophenylethyl trithiocarbonate3',4,4'-trifluoro-3-butenyl-3-p-chlorophenyl ethyl dithiocarbonateN-ethyl-N-a-hydroxymethyhs- (3,4,4-trifiuorobutenyl- 3 thiolcarbamateN-n-butyl-N-y-hydroxy propyl-S- 3,4,4-trifluorobuteny1- 3dithiocarbamate N-alkyl-N-fi-hydroxybutyl-S- 3,4,4-trifiuorobutenyl-3)dithiocarbamate S- 3,4,4-trifluorobutenyl-3 l-tetramethyleneiminecarbothiolate S- 3,4,4-trifluorobutenyl-3 -1-pentamethyleneiminecarbothiolate S- 3 ,4,4'-trifiuorobutenyl-3 -N,N-dicyclobutyldithiocarbamate S- (3 ,4,4'-trifluorobutenyl-3 -N,N-dicyclopentyldithiocarbamate S- 3 ',4',4'-trifiuorobutenyl-3 -N,N-dicyclobutylthiolcarbamate.

As previously pointed out, the herein described toxicants produced inthe above-described manner are biologically active entities which areuseful and valuable in the control of various organisms. The compoundsof the invention were tested as nematocides in the following manner.

Nematocide evaluation test.This test determines a candidates action onroot knot nematodes (Meloidogyne, sp.) in soil. One-pound portions ofsoil infested with rootknot nematodes were placed in quart jars. Thechemical to be tested was pipetted into the nematode infested soil atvarious dilutions of from to 1 part per million (p.p.m.) or untilactivity was lost. After mixing the candidate compound into the soil,the soil was sealed for 48 hours. The treated soil was then placed inpaper containers and allowed to stand in a greenhouse one Week forairing.

At the end of this time, a tomato plant was transplanted into the soil.The root-knot nematodes attack the tomato plant roots if they survivethe chemical treatment, and cause swelling or knots on the roots. Fourweeks after treatment, the plant was removed from the soil and the rootsinspected. The lowest concentration which prevented nematode developmentwas recorded. The results are set forth in the following table:

TABLE II Nematode Nematode Compound control, Compound contr numberp.p.m. number p.p.m

Nora.-Parentheses indicate partial control.

The compounds of the present invention may be used as effectivenematocides and may be applied in a variety of ways at variousconcentrations. In practice, the compounds are usually formulated withan inert nematocidal adjuvant, utilizing methods well known to thoseskilled in the art, thereby making them suitable for application asdusts, sprays or drenches. The amount applied will depend upon thenature of the nematode to be controlled and the rate of application mayvary from =1 to 50 pounds per acre. One particularly advantageous way ofapplying the nematocidal composition comprising the adjuvant and aneffective amount of a compound of the present invention is as a spray,drench or dust followed by incorporation.

Herbicidal screening tests As previously mentioned, the herein describedcompounds produced in the above-described manner are phytotoxiccompounds which are useful and valuable in controlling various plantspecies. Compounds of this invention are tested as herbicides in thefollowing manner.

Pre-emergence herbicide test.-On the day preceding treatment, seeds ofseven diflerent plant species are planted in individual rows using onespecies per row across the width of the flat. The seeds used are hairycrabgrass (Digitaria sanguinalis (L.) Scop), Annual bluegrass (Poa annua(L.)), watergrass (Echinochloa crusgalli (L.) Beauv.), California redoat (Avena sativa (=L.)) redroot pigweed (Amaranzhus retroflexus (L),Indian mustard (Brassica juncea (L.) Coss.) and curly dock (Rumexcrispus (L.). Ample seeds are planted to give about 20 to 50 seedlingsper row, after emergence, depending on the size of the plants. The flatsare watered after planting. The spraying solution is prepared bydissolving 50 mg. of the test compound in 3 ml. of a solvent, such asacetone, containing 1% Tween 20 (polyoxyethylene sorbitan monolaurate).The following day, each flat is sprayed at the rate of 20 pounds of thecandidate compound per 80 gallons of solution per acre. An atomizer isused to spray the solution on soil surface. The flats are placed in agreenhouse at 80 F. and watered regularly. Two weeks later, the degreeof weed control is determined by comparing the amount of germination andgrowth of each weed in the treated flats with weeds in several untreatedcontrol flats. The rating system is as follows:

=no significant injury (-15 percent control) +=slight injury (25-35percent control) ++=moderate injury (55-65 percent control) +++=severeinjury or death (85.100 percent control) An activity index is used torepresent the total activity on all seven weed species. It is the sum ofthe number of plus marks, so that an activity index of 21 representscomplete control of all seven weeds. The resultsof this test arereported in Table II.

Post-emergence herbicide test.Seeds of six plant species including hairycrabgrass, watergrass, California red oats, Indian mustard, curly dockand pinto beans (Phaseolus vulgaris), are planted in flats as describedabove for pre-emergence screening. The flats are placed in thegreenhouse at 72-85" F. and watered daily with a sprinkler. About 10 to14 days after planting when the primary leaves of the bean plant arealmost fully expanded and the first trifoliate leaves are just startingto form, the plants are sprayed. The spray is prepared by Weighing out50 mg. of the test compound, dissolving it in 5 ml. of acetonecontaining 1% Tween 20 (polyoxy-ethylene sorbitan monolaurate) and thenadding 5 ml. of water. The solution is sprayed on the foliage using anatomizer. The spray concentration is 0.5% and the rate would beapproximately 20 lb./acre if all of the spray were retained on the plantand the soil, but some spray is lost so it is estimated that theapplication rate is approximately 12.5 lb./acre.

Beans are used to detect defoliants and plant growth regulators. Thebeans are trimmed to two or three plants per fiat by cutting off theexcess weaker plants several days before treatment. The treated plantsare placed back in the greenhouse and care is taken to avoid sprinklingthe treated foliage with water for three days after treatment. Water isapplied to the soil by means of a slow stream from a watering hose takencare not to wet the foliage.

Injury rates are recorded 14 days after treatment. The rating system isthe same as described above for the preemergence test where and are usedfor the different rates of injury and control. The injury symptoms arealso recorded. The maximum activity index for complete control of allthe species in the postemergence screening test is 18 which representsthe sum of the plus marks obtained with the six plant species used inthe test. The herbicide activity index is shown in Table III.

TABLE IlI.-HE RBICIDAL ACTIVITY SCREENING RESULTS Herbicidal activityindex i Pre-emergence Post-emergence (20 1b./a.) (1 lb.

Conip ound number:

1 21=85100% control of all 7 weed Species tested preemergence, 18=85control of all 6 weed species tested postemergence.

2 Green toxtail (Setaria vividis (L.) Beauv.) was substituted for Annualbluegrass (Poa amwa (L.)).

Compound Number 25, the N,N-di-isopropyl amino analog of the oxygencontaining members is of particular utility in controlling wild oats(Avena fatua (L.)) in wheat and barley crops. When this compound isincorporated into the soil preplant, no injury was observed in the cropswhile control of the weed specie Was effected. The present inventionfurther relates to a selective herbicidal composition useful for thecontrol of wild oats in wheat and barley crops which comprisesS-(3,4,4-trifluoro- 3-butenyl)N,N-di-isopropylthiolcarbamate and aninert herbicidal adjuvant.

The compounds of the present invention are used as pre-emergence orpost-emergence herbicides and are ap plied in a variety of ways atvarious concentrations. In practice, the compounds are formulated withan inert carrier, utilizing methods well known to those skilled in theart, thereby making them suitable for application as dusts, sprays, ordrenches and the like in the form and manner required. The mixtures canbe dispersed in water with the aid of a wetting agent or they can beemployed in organic liquid compositions, oil and water, water in oilemulsions, with or without the addition of wetting, dispersing oremulsifying agents. The amount applied depends upon the nature of theseeds or plants to be controlled and the rate of application varies from1 to approximately 50 pounds per acre.

The phytotoxic compositions of this invention are applied to the plantsin the conventional manner. Thus, the dust and liquid compositions canbe applied to the plant by the use of power-dusters, boom and handsprayers and spray-clusters. The compositions can also be applied fromairplanes as a dust or a spray because they are effective in very lowdosages. In order to modify or control growth of germinating seeds oremerging seedlings, as a typical example, the dust and liquidcompositions are applied to the soil according to conventional methodsand are preferably distributed in the soil to a depth of at least /2-inch below the soil surface. It is not necessary that the phytotoxiccompositions be admixed with the soil particles and these compositionscan be applied merely by spraying or sprinkling the surface of the soil.The phytotoxic compositions of this invention can also be applied byaddition to irrigation water supplied to the field to be treated. Thismethod of application permits the penetration of the compositions intothe soil as the water is absorbed therein. Dust compositions, granularcompositions or liquid formulations applied to the surface of the soilcan be distributed below the surface of the soil by conventional meanssuch as discing, dragging or mixing operations.

The phytotoxic compositions of this invention can also contain otheradditaments, for example, fertilizers, pesticides and the like, used asadjuvant or in combination with any of the above-described adjuvants.Other phytotoxic compounds useful in combination with theabove-described compounds include for example, 2,4 dichlorophenoxyaceticacids, 2,4,5 trichlorophenoxyacetic acid, 2 methyl 4 chlorophenoxyaceticacid and the salts, esters and amides thereof; triazine derivatives,such as 2,4 bis(3 methoxypropylamino) 6 methylthio S- triazine; 2 chloro4 ethylamino 6 isopropylamino- S triazine, and 2 ethylamino 4isopropylamino 6- methylmercapto S triazine, urea and 3 (p chlorophenyl)1,1 dimethyl urea and acetamides such as N,N diallyl oc chloroacetamide,N (cc chloroacetyl) hexamethylene imine, andN,N-diethyl-a-bromoacetamide, and the like; benzoic acids such as3-amino2,5dichlorobenzoic and; thiocarbamates, such as S-propyldipropylthiocarbamate; S-ethyl-dipropylthiocarbamate, S- ethylcyclohexyl ethyl thiocarbamate, S-ethyl hexahydro 1H azepine 1carbothioate and the like. Fertilizers useful in combination with theactive ingredients include for example, ammonium nitrate, urea andsuperphosphate. Other useful additaments include materials in whichplant organisms take root and grow, such as compost, manure, humus, sandand the like.

The concentration of a compound of the present invention, constitutingan eflective amount in the best mode of administration in the utilitydisclosed is readily determinable by those skilled in the art. Variouschanges and modifications are possible Without departing from the spiritapparent to those skilled in the art to which it pertains. It isaccordingly intended that the present invention shall only be limited bythe scope of the claims.

What is claimed is:

1. Compounds of the formula to claim 1 in which X is to claim 1 in whichX is to claim 1 in which X is to claim 1 in which X is to claim 1 inwhich X is References Cited UNITED STATES PATENTS 3,335,182 8/1967Curtis et al. 71-101 3,161,498 12/1964 Price et al. 260566 2,396,5133/1946 Jones 7l-98 FOREIGN PATENTS 619,282 3/1961 Italy 71-100 LEWISGOTTS, Primary Examiner G. HOLLRAH, Assistant Examiner U.S. Cl. X.R.

71-72, 76, 77, 88, 98, 99, Dig. 1; 424298, 322

